O,s,n-tri-aliphatic hydrocarbon-thiono-thiolphosphoric acid ester amides

ABSTRACT

O,S,N-TRI-ALIPHATIC HYDROCARBON-THIONOTHIOLPHOSPOHRIC ACID ESTER AMIDES OF THE GENERAL FORMULA   R-O-P(=S)(-NH-R1)-S-R2   IN WHICH R, R1 AND R2, WHICH MAY BE THE SAME OR DIFFERENT, EACH IS AN ALKYL, ALKENYL OR ALKYNYL RADICAL WITH UP TO 6 CARBON ATOMS, OPTIONALLY SUBSTITUTED WITH AT LEAST ONE HALO, PHENYL, CYANO, ALKOXY, ALKYLMERCAPTO, PHENYLMERCAPTO OR NAPHTHYLMERCAPTO RADICAL, THE MERCAPTO RADICALS BEING OPTIONALLY CHLORO- OR CYANO-SUBSTITUTED, WHICH POSSESS NEMATOCIDAL, INSECTICIDAL, ACARIDICAL, FUNGICIDAL AND MAMMALIAN-REPELLENT PROPERTIES.

3,793,407 0,S,N-TRI-ALIPHATIC HYDROCARBON-THIONO- THIOLPHOSPHORIC ACIDESTER AMIDES Claus Stolzer, Wuppertal-Vohwinkel, Bernhard Homeyer,Opladen, Ingeborg Hammann, Cologne, and Gunter Unterstenhofer, Opladen,Germany, assignors to Bayer Aktiengesellschaft, Leverkusen, Germany NoDrawing. Filed July 6, 1971, Ser. No. 160,185 Claims priority,application Germany, July 11, 1970, P 20 34 475.6 Int. Cl. A0111 9/36;C07f 9/24 US. Cl. 260--948 4 Claims ABSTRACT OF THE DISCLOSURE Thepresent invention relates to and has for its objects the provision ofparticular new O,S,N-tri-aliphatic hydrocarbon-thionothiolphosphoricacid ester amides, i.e. 0,8, and N-(mono) -alkyl, alkenyl oralkynyl-thionothiolphosphoric acid ester amides, which possessnematocidal, insecticidal, acaricidal, fungicidal andmammalian-repellent properties, active compositions in the form ofmixtures of such compounds with solid and liquid dispeisible carriervehicles, and methods for producing such compounds and for using suchcompounds in a new way especially for combating pests, e.g. nematodes,insects, acarids, fungi and destructive mammals, especially nematodes,insects and acarids, with other and further objects becoming apparentfrom a study of the within specification and accompanying examples.

It is known from German published specification 1,032,247 and Germanpatent specifications 830,509 and 917,668 that certain0,0,S-trialkyl-thionophosphoric acid esters, for example the0,0-diethyl-S-Z-ethylmercaptoethyl ester of thionothiolphosphoric acid(Compound A), possess insecticidal and acaricidal properties.

The present invention provides, as new compounds, the O-alkyl (alkenyl,alkynyl)-S-alkyl(alkenyl, alkynyl)-N- monoalkyl(alkenyl,alkynyl)-thionothiolphosphoric acid ester amides of the general formulaROS R NH in which R, R and R which may be the same or different, each isan alkyl, alkenyl or alkynyl radical with up United States Patent to 6carbon atoms, optionally substituted with at least one halo, phenyl,cyano, alkoxy, alkylmercapto, phenylmercapto or naphthylmercaptoradical, the mercapto radicals being optionally chloroorcyano-substituted.

The compounds of the Formula I have been found to exhibit goodinsecticidal and acaricidal activity and a particularly strongnematocidal activity, as well as also exhibiting fungicidal activity anda repellent action towards destructive mammals.

The present invention also provides a process for the preparation of acompound of the Formula I, in which an O-alkyl(alkenyl, alkynyl)-N-monoalkyl(alkenyl, alkynyl) amido-thionothiolphosphoric acid ester salt ofthe general formula ROS i S M R N H (II) in which R and R have themeanings stated above, and M stands for an alkali metal equivalent, analkaline earth metal equivalent or an optionally alkyl-substitutedammonium equivalent,

is reacted with a compound of the general formula in which R has themeaning stated above, and Hal stands for a halogen atom, preferably achlorine or bromine atom.

Surprisingly, the novel thionothiolphosphoric acid ester amides of theGeneral Formula I possess not only very good insecticidal and acaricidalproperties, but also a considerably higher nematocidal activity than theknown 0,0,S-trialkyl-phosphoric acid esters which are chemically themost closely comparable compounds of the same type of activity. Thecompounds of the invention are therefore an enrichment of the art.

If the potassium salt of O-ethyl-N-monoisopropylthionothiolphosphoricacid ester amide and l-chloro-Z- ethyl-mercaptoethane are used asstarting materials, the reaction may be represented by the followingequation:

KCl

iCaH1NH branched-chain alkyl groups with 1-4 carbon atoms and alkenylgroups with 24 carbon atoms, which alkyl and alkenyl groups each carryat least one substituent selected from the group consisting of chlorineand bromine atoms and cyano, lower alkoxy, lower alkylmercapto,phenylmercapto and naphthylmercapto radicals, the said mercapto radicalsbeing optionally chloroor cyano-substituted. The preferred cyclic alkylradical is cyclohexyl.

As examples of the starting materials of the Formula II, there may bementioned the potassium, sodium and ammonium salts of O-methyl-N-methyl,O-methyl-N- ethyl, O-methyl-N-isopropyl-, O-methyl-N-n-propyl-, O-methyl-N-(n-, iso-, sec.- or tert.-)butyl-, O-ethyl-N- methylO-ethyl-N-ethyl-, O-ethyl-N-n-propyl-, O-ethy1-N- isopropyl-,-ethyl-N-(n-, iso-, sec.- or tert.-)'butyl-, O-npropyl-N-methyl-,O-n-propyl-N-ethyl-, o-n-propyl-N-npropyl-, O-n-propyl-N-isopropyl,O-n-propyl-N-(n-, iso-, sec.- or tert.-)butyl-, O-isopropyl-N-methyl-,O-isopropyl- N-ethyl-, O-isopropyl-N-n-propyl-,O-isopropyl-N-isopropyl-, O-isopropyl-N-(n-, iso-, sec.- or tert.-)butyl, O-(n-, iso,- sec.- or tert.-)butyl-N-methyl, O-(n-, iso-, sec.-or tert.-)butyl-N-ethyl and O-(n-, iso-, sec.- or tert.-)butyl-N-isopropyl-thionothiolphosphoric acid ester amides.

The preparative process is preferably carried out with the use of asolvent or diluent, for which purpose practically all inert organicsolvents and diluents are suitable, especially aliphatic and aromaticoptionally possibly chlorinated hydrocarbons, such as benzene, toluene,xylenes, benzine, methylene chloride, chloroform, carbon tetrachlorideand chlorobenzene; ethers, such as diethyl ether, dibutyl ether anddioxane; ketones, such as acetone and methylethyl, methylisopropyl andmethylisobutyl ketones; nitriles, such as acetonitrile; and alcohols,such as methanol, ethanol and propanol. In some cases also water may beused as solvent or diluent. The reaction temperatures can be variedwithin a fairly wide range: in general, the reaction is effected atabout 0 to 100 0., preferably about to C.

The reaction is, in general, carried out at normal pressure.

When carrying out the process of the invention, the salts of the FormulaII and the halogen compounds of the Formula III are, in most cases, usedin equimolar amounts. An excess of one or the other of the reactantsbrings no substantial advantages. Preferably, the reaction is effectedin one of the above-mentioned solvents at about 30 to 40 C.: thereaction mixture is thereafter stirred for some hours and worked upaccording to any customary method.

The substances according to the invention are obtained in most cases inthe form of colorless to slightly yellowcolored, viscous,water-insoluble oils which in many cases cannot be distilled withoutdecomposition but which can, by so-called slight distillation, that isby longer heating to moderately elevated temperatures under reducedpressure, be freed from the last volatile components and in this way bepurified. For their characterization, the refractive index is especiallysuitable. Solid compounds are characterized by their melting points. Asalready mentioned, the compounds according to the invention arecharacterized by outstanding nematocidal, insecticidal and acaricidalproperties. They possess at the same time a good efiectiveness againstboth sucking and biting insects, Diptera, mites, as well as a systemicactivity. In addition, they also show a fungitoxic effectiveness againstphytopathogenic fungi, for example Pirz'cularia oryzae, as well as arepellent action towards destructive mammals. The products, therefore,may be used with success in crop protection and the protection of storedproducts, as well as in the hygiene field, against the most diverseanimal pests.

To the sucking insects contemplated herein there belong, in the main,aphids (Aphidae) such as the green peach aphid (Myzus persicae), thebean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi),the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphumsolanifolii), the rosy apple aphid (Sappaphis mali), the mealy plumaphid (Hyalopterus arundinis), the currant gall aphid (Cryptomyzuskorschelti), and the cherry black-fly (Myzus cerasi); in addition,scales and mealybugs (Coccina), for example the oleander scale(Aspidioms hederae) and the soft scale (Lecanium hesperidum) as Well asthe grape mealybug (Pseudococcus maritimus); thrips (Thysanoptera), suchas Hercz'nothrips femoralis, and bugs, for example the beet bug (Piesmaquadrata), the red cotton bug (Dysdercus intermedius), the bed bug(Cimex leclularius), the assassin bug (Rhodnius prolixus) and Chagas bug(Triatoma infestans) and, further, cicadas, such as Euscelius bilobatusand Nephotettix bipunctatus; and the like.

In the case of the biting insects contemplated herein, above all thereshould be mentioned butterfly caterpillars (Depidoptera) such as thediamond-back moth (Plutella maculipennis), the gypsy moth (Lymantriadispar), the brown-tailed moth (Euproctis chrysorrhoea) and tentcaterpillar (Malacosoma neustria); further, the cabbage moth (Mamestrabrassicae) and the cutworm (Agrotz's segetum), the large white butterfly(Pieris brassicae), the small winter moth (Cheimatobia brumata), thegreen oak tortrix moth (Tortrix viridana), the fall armyworm (Laphygmafrugidperda) and cotton worm (Prodenia litura), the ermine moth(Hyponomeuta gadella), the Mediterranean flour moth (Ephestiakiihniella) and greater wax moth (Galleria mellonella); and the like.

Also to be classed with the biting insects contemplated herein arebeetles (Coleoptera), for example the granary weevill (Sitophilusgranarius=Calandra granaria), the Colorado beetle (Leptinotarsadecemlineata), the dock beetle (Gastrophysa viria'ula), the mustardbeetle (Phaedon cochleariae), the blossom beetle (Meligethes aeneus),the raspberry beetle (Byturus tomentosus), the bean weevil(Bruchidius=Acanthoscelides obtectus), the leather beetle (Dermestesfrischi), the khapra beetle (Trogoderma granarium), the flour beetle(Tribolium castaneum), the northern corn billbug (Calandra or Sitophiluszeamais), the drugstore beetle (Stegobium paniceum), the yellow mealworm(Tenebrio molitor) and the sawtoothed grain beetle (Oryzaephilussurinamensis), and also species living in the soil, for examplewireworms (Agriotes spec.) and larvae of the cockchafer (Melolonthamelolontha); cockroaches, such as the German cockroach (Blattellagermanica), American cockroach (Periplaneta americana), Madeiracockroach (Leucophaea or Rhyparobia maderae), oriental cockroach (Blattaorientalis), the giant cockroach (Blaberus giganteus) and the blackgiant cockroach (Blaberus fucus) as well as Henschoutedenia flexivitta;further, Orthoptera, for example the house cricket (Acheta domesticus);termites such as the eastern subterranean termite (Reticulitermsflavipes) and Hymenoptera such as ants, for example the garden ant(Lasius nz'ger); and the like.

The Diptera contemplated herein comprise essentially the flies, such asthe vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly(Ceratitis capitata), the house fly (Musca domestica), the little housefly (Fannia canicularis), the black bow fly (Phormia regina) andbluebottle fly (Calliphora erythrocephala) as well as the stable fly(Stomoxys calcitrans); further, gnats, for example mosquitoes such asthe yellow fever mosquito (Aedes aegypti), the northern house mosquito(Culex pipiens) and the malaria mosquito (Anopheles stephensi); and thelike.

With the mites (Acarina) contemplated herein there are classed, inparticular, the spider mites (Tetranychidae) such as the two-spottedspider mite (Tetranychus telarius=Tetranychus althaeae or Tetranychusurticae) and the European red mit (Paratetranychus pilosus=Pan0nychusulmi), gall mites, for examples the black current gall mite (Eriophyesribis) and (tarsonemids, for example the broad mite (Hemitarsonemuslatus) and the cyclamen mite (Tarsonemus pallidus) finally, ticks, suchas the relapsing fever tic-k (Ornithoa'orus moubata); and the like.

When applied against pests harmful to health and pests of storedproducts, especially flies and mosquitoes, the compounds of theinvention are also distinguished by an outstanding residual activity onwood and clay, as well as a good stability to alkali on limedsubstrates.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e. diluents, carriers or extenders ofthe type usable in conventional pesticide formulations or compositions,e.g. conventional pesticide dispersible carrier vehicles such as gases,solutions, emulsions, suspensions, emulsifiable concentrates, spraypowders, pastes, soluble powders, dusting agents, granules, etc. Theseare prepared in known manner, for instance by extending the activecompounds with conventional pesticide dispersible liquid diluentcarriers and/or dispersible solid carriers optionally with the use ofcarrier vehicle assistants, e.g. conventional pesticide surface-activeagents, whereby, for example, in the case where water is used asdiluent, organic solvents may be added as auxiliary solvents. Thefollowing may be chiefly considered for use as conventional carriervehicles for this purpose: aerosol propellants which are gaseous atnormal temperatures and pressures, such as freon; inert dispersibleliquid diluent carriers, including inert organic solvents, such asaromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.),halogenated, especially chlorinated, aromatic hydrocarbons (e.g.chlorobenzenes, etc.), parafiins (e.g. petroleum fractions), chlorinatedaliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g.methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine,etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.),amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethylsulfoxide, etc.), ketones (e.g. acetone, etc.) and/or 'water; as well asinert dispersible finely divided solid carriers, such as ground naturalminerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calciumcarbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) andground synthetic minerals (e.g. highly dispersed silicic acid,silicates, e.g. alkali silicates, etc.); Whereas the following may bechiefly considered for use as conventional carrier vehicle assistants,e.g. surface-active agents, for this purpose: emulsifying agents, suchas non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxideesters of fatty acids, polyethylene oxide ethers of fatty alcohols,al=kyl sulfonates, aryl sulfonates, etc., and especially alkylarylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/ordispersing agents, such as lignin, sulfite waste liquors, methylcellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as acaricides, insecticides,fungicides, bactericides and nematocides, or rodenticides, herbicides,fertilizers, growth-regulating agents, etc., if desired, or in the formof particular dosage preparations for specific application madetherefrom, such as solutions, emulsions, suspensions, powders, pastes,and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in. an amount substantially between about 01-95% by weight andpreferably 0.590% by weight, of the mixture, whereas carrier compositionmixtures suitable for direct application or field application generallycontemplate those in which the active compound is present in an amountsubstantially between about 0.0001%, preferably 0.011%, by weight of themixture. Thus the present invention contemplates over-all compositionswhich comprise mixtures of a conventional dispersible carrier vehiclesuch as (1) a dispersible inert finely divided carrier solid, and/or (2)a dispersible carrier liquid such as an inert organic solvent and/orwater preferably including a surface-active eifective amount of acarrier vehicle assistant, e.g. a surface-active agent, and an amount ofthe active compound which is effective for the purpose in question andwhich is generally between about 0.0001%, and preferably 0.01-95%, byweight of the mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50-100 microns, oreven less, i.e. in mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 15 to 1000 g./hectare, preferably 40to 600 g./hectare, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95% by weight of the activecompound or even the active substance alone, e.g. about 20100% by weightof the active compound.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. nematodes, insects,acarids, fungi and destructive mammals and more particularly methods ofcombating at least one of nematodes, insects and acarids which comprisesapplying to at least one of correspondingly (a) such nematodes, (b) suchinsects, (c) such acarids, ,(d) such fungi and (f) the correspondinghabitat thereof or of destructive mammalian pests, i.e. the locus to beprotected, a correspondingly combative or toxic amount, i.e. anematocidally, insecticidally, acaricidally, fungicidally, ormammalian-repellent effective amount of the particular active compoundof the invention alone or together with a carrier vehicle as notedabove. The instant formulations or compositions are applied in the usualmanner, for instance by spraying, atomizing, vaporizing, scattering,dusting, Watering, squirting, sprinkling, pouring, fumigating, and thelike.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particularnew compounds of the present invention are illustrated, withoutlimitation, by the following examples:

EXAMPLE 1 Myzus test (contact action) Solvent: 3 parts by weight acetoneEmulsifier: 1 part by weight alkylarylpolyglycol ether To produce asuitable preparation of active compound, 1 part by weight of the activecompound is mixed with the stated amount of solvent containing thestated amount of emulsifier and the concentrate is diluted with water tothe desired concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested withpeach aphids (Myzus persicae) are sprayed with the preparation of theactive compound until dripping wet.

After the specified periods of time, the degree of destruction isdetermined as a percentage: 100% means that all the aphids are killedwhereas 0% means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds, theevaluationtimes and the results can be seen from the following Table 1:

TABLE 1.

(Myzus test) Concentration of active Degree of compound destruction inpercent in percent Active compounds by weight after 1 day C3H5O S 0.1100 v\II 0. 01 100 P-S'-CHaS-CHa' 0.001 s on -N11 I 021150 3 0. 1 100.\Il 0. 01 98 W I-S-CH2-CH2 S-C2Hs 0.001 CHI-7N3 CzHiO s CHZO] o. 1 100\n 0.01 100 PSCHzSC-CN 0.001 09 GHr-NH CH;

CgH O S 0.1 100 \II 0.01 /P--s0H,-s-o,m 0.001 05 (CH0)2CHNH CZHsO SCHzCl \ll, 0.1 100 -S-CHz-S-C-CN 0.01 98 1 0.001 05 (CHz)aCH-NH CH1CzHaO S 0.1 100 0.01 00 PS-GHz-CHaSC:Hs 0.001

(CH1)2CHNH CgHsO s 0.1 0. 01 99 PS-CH:CN 0.001 75 i-CzHv-NH 021100 8 0.1 100 \ll 0. 01 100 I P-S-CHr-CHr-S-C:Hn 0.001 50 CH2=CHCHr-NH 01 (3-0110 S 0.1 100 0. 01 100 P S CH:CH:-S C2Hs 0. 001 75 i-C:H1NH

EXAMPLE 2 of approximately 10-30 cm., are sprayed with the preparationof the active compound until dripping wet. These Tetranychus test beanplants are heavily infested with spider mites (Tetranychus urticae) inall stages of development. I 0 After the specified periods of time, theeffectiveness of Solvent: 3 parts by weight acetone Emulsifier: 1 partby weight al'kylarylpolyglycol ether To produce a suitable preparationof active compound, 1 part by weight of the active compound is mixedwith H the stated amount of solvent containing the stated amount 15 noneof the splder mites are killed.

the preparation of active compound is determined by counting the deadmites. The degree of destruction thus obtained is expressed as apercentage: 100% means that all the spider mites are killed whereas 0%means that The active compounds, the concentrations of the activecompounds, the evaluation times and the results can be seen from thefollowing Table 2:

l with soil which is heavily infested with the test nematodes. Theconcentration of the active compound in the preparation is ofpractically no importance; only the amount of TABLE 2 (Tetranychus test)Concentrations of active Degree of compound destruction in percent inpercent Active compounds by weight after 2 days 0. 1 95 0 01 0(ClH50)flP-S -CH1CH:-S-CHz-CH:

CQHAO S 0. 1 100 \ll 0. 01 100 P-S-CHrS-CgHe CHr-NH C2Hs0 S 0. 1 99 0.0]. 98 S --CH:C Ha-Cl (CH1) aCH-NH CIHBO\IS 00.01 100 90 l S 0 HP 8 C2 l(C H) aCH-NH CaHuO SI CHQCI 0. 1 100 SCHa-SC--CN 0.01

(CH1) rCH-N CHI 0 1150 8 0. 1 100 0. 01 100 P- S -C HaCHa- S C 2H5 (0Hz) a C H-NH EXAMPLE 3 Critical concentration test Test nematode:Meloidogyne sp Solvent: 3 parts by weight acetone Emulsifier: 1 part byweight alkylarylpolyglycol ether.

active compound per unit volume of soil, which is given To produce asuitable preparation of active compound, 1 part by weight of activecompound is mixed with the stated amount of solvent, the stated amountof emulsifier is added and the concentrate is diluted with same manner.

water to the desired concentration.

The preparation of active compound is intimately mixed in p.p.m., isdecisive. The soil is filled into pots, lettuce is sown in and the potsare kept at a green house temperature of 27 C. After 4 Weeks, thelettuce roots are examined for infestation with nematodes, and thedegree 50 of effectiveness of the active compound is determined as apercentage. The degree of efiectiveness is when infestation iscompletely avoided; it is 0% when the infestation is exactly the same asin the case of the control plants in untreated soil which has beeninfested in the The active compounds, the amounts applied and theresults can be seen from the following Table 3:

TABLE 3 (Nematocldes Meloidogmze incognito) Degree of destruction inpercent with a concentration 01 active compound in p.p.m. 0t-

Degree of destruetion in percent with a concentration or active compoundin p.p.m.oi- Active compound so 40 20 10 a a 1.25

l '-SCH:$CzHl I iCaH1--NH l SGH,OH;SC,H

lCtH1NH -BCH2-C=CH CHa-NH C7H50 S 100 100 100 99 98 98 90 \IP!-SCHR-CHICI lCaH1-NH ClHO S 98 90 0 lI"S-CHzCHzSCzH CZHB (known) (A) Thefollowing examples will illustrate the compounds The mixture isafterwards stirred over-night at (2.; it

of the invention.

is poured into water; the mixture is taken up in benzene;

EXAMPLE 4 the organic phase is washed neutral with water; it is driedCQHBO S over sodium sulfate; the drying agent is filtered 01f; the

\II 8 c H filtrate is concentrated and the residue obtained is dis- S 2m 40 tilled. 86.3 g. (75.0% of theory) of O-ethyl-S-(Z-ethylamercapto-ethyl) N-monoisopropylthionothiolphosphoric To 97.2 g. (0.44mole) of the sodium salt of O-ethyl-N-monoisopropylthionothiolphosphoric acid ester amide in 300 cc. ofacetonitrile there are added slowly, at 40, 49.8 g. (0.4 mole) ofl-chloro-2-ethyl-mercapto-ethane.

Constitution CaHsO Physical properties I CzHsO iCaHr-NH ChHsOTABLE--Continued i lhysical properties i- C a l 3 my, Tum-5 k"; 1.5719,!

CzHrO S It will be appreciated that the instant specification andexamples are set forth by way of illustration and not limitation, andthat various modifications and changes may be made without departingfrom the spirit and scope of the present invention. What is claimedis: 1. A thionothiolphosphoric acid ester amide of the formula P-s-R=RNH (I) in which R and R each is an alkyl or alkenyl radical with up to4 carbon atoms, and R is an alkyl radical with 1-4 carbon atoms carryinga lower alkylmercapto, phenylmercapto or naphthylmercapto radical, themercapto radicals being optionally chloro-substituted. 2. Compoundaccording to claim 1 wherein such compound isO-ethyl-S-2-ethylmercaptoethyl-N-isopropyl-thionothiolphosphoric acidester amide of the formula CzHrO S (CHahCH-NH 3. Compound according toclaim 1 wherein such com- TABLE-Contlnued Constitution Physicalproperties 0211.0 s 'nn"=1.5538.

@NH S--CH:CHz-SOzHa 0,11 0 s nv"=1.5512.

/P\ @NH s-omo E on CzHsO S 'llD' =1.5477.

/P\ @NH s-om-cm-ol CzH O S 71p =1.5551.

NCOHz-OHzNH s-om-oHT-s-clrn CzHgO S 72D'7-5==1.5546.

NO-OHz-CHr-NH s-om-c B011 flD =L55IZII pound is OethylS-ethylmercaptomethyl-N-mcthyl-thi0- thiolphosphoric acid esteramide of the formula CzHaO S i SCH2SCzHs CHE-NH 4. Compound according toclaim 1 wherein such compound is Oethyl-S-Z-ethylmercaptoethyl-N-methyl-thionothiolphosphoric acid esteramide of the formula CHr-NH References Cited UNITED STATES PATENTS3,019,250 1/1962 Kayser et al 260948 X 3,159,665 12/1964 Blair 2609492,881,201 4/1959 Schrader 260949 X 3,171,853 3/1965 Lorenz et al. 260948LEWIS GOTTS, Primary Examiner R. L. RAYMOND, Assistant Examiner US. Cl.X.R.

UNITED 513M155 lAlbM OFFICE CLKTIFICATE or comus'c'moN 0 Patent No.$793,407 Dated February 19, 197 4 Inventor(s) CLAUS STOLZER ET AL I(Dame 1 of 2) It is certified that error appears in the above-identifiedpatent am that said Letters Patentare hercby corrected as shown below:

Col. line 17, change "Depidoptera" to Lepidoptera QCol. 4, line 26,change "gadella" to padella Col. 4, line 31, correct spelling of"weevil".

Col. A, line 50, change "fucus" to fuscus Col. 4, line 5 change "terms"to 'termes Col. 4, line 71, change "mit" to mite Col. 13, TableCompound(l2).,cancel between C" and CH and substitute therefor 5"; lastcolumn of Table,

6,. 21.5 change n to n n 19 OCol. 13, Table Compound(ll),change n to nCol. 15, Table Compound (6), correct; formula to read as follows:

UNH'ILD SIA'IJ'JS PATENT, OFFICE Cr-JRTIMCATE OF CORKEC'HON Patent No,3,793,407 Dated F b 9 1974 Inventor) Claus Stolzer, et al (Page 2 f 2)It is certified that error appears in the aboyc-identiied patent andthat said Letters Patentare hereby corrected as shown below:

C010 15, Table Compound (25) correct formula to read as follow x -s-[I-CN iCanP-NH Col; 15, Table Compound (34) chang H D .5n D 7.5 0

Col. 17, Table- Compound (41) cancel between 2" and "CH" and substitutetherefor E Cole 19, Table Compound (47 correct formula to read as folloThis certificate supersedes Certificate of Correction issued January 28,1975.

Signed and Scaled thisthirtieth D f March 1976 [SEAL] Arrest:

Lm RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ofParents and Trademarks 2:33;" um'rm s'm'iazaas Pmm'r 0F m;

" TTIHGATE F CHEUH Patenc No, 3 793 7 Domed February 1974 Inven m CLAUSSTOLZER ET AL (Helge 1 of 2} It is oertified mhat error appeamdn theaboyo idemifiied patent and that said Letters Potent-am hemby correctedM shown bolows line 3.7 change Depidoptora to w Lepidoptara w line 26change "gadella' to padella Col. 4, lino 31,, correct spelling ofweevilH A line 50, change foams to 4m fuscus 4, line .54, change "termsto M termos' 4, line 71, change "mit" to M mite C01. 13 TableCompounfllh oancel between C" and CH and substituto therefor M :3 5 lastoolumn of Table,

nzms to M D2165 Mo C01. 13, Tabl Compoundfll) ,change "n to M a changeCol. 15; Table Compound (6),, correct formula to read as follows:

UNITED S'I'A'I'JSS PATENT OFFICE CERTIFICATE ()F CQRRECTION Patent No.07 Dated Inventor) I (page 2 of 2) It is certified that: errorappears-fin the aboye-idenrified patent and that: said LettersPatentarehereby corrected as shownbelow:

001. 15, Table Compoond (2S) correct: formula to read as follow' 0,1110%cm-m "5 'r-an-cn (Cunt-NB C201.' 15,. Table Compound (34) I chaoge n 7.5" ts n Col. 17, Table:- Compound (41) 'cahcel between "CH and "CH" andsubstitute therefor T:

C01 19, Table Compound (47) correct formoia toread as follows clmo a Pcms-cm-cm-Nn a-(- H (m Signed arid sealed this-28th day of Jatiuery1975. I

(SEAL) Attest:

McCOY M. GIBSON JR. r c. MARSHALL DANN: Attesting Officer Commissionerof, Patents

